CN113501993A - Mn (manganese)2+Cesium-lead-halogen-doped perovskite quantum dot film and preparation method thereof - Google Patents

Mn (manganese)2+Cesium-lead-halogen-doped perovskite quantum dot film and preparation method thereof Download PDF

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CN113501993A
CN113501993A CN202110793571.5A CN202110793571A CN113501993A CN 113501993 A CN113501993 A CN 113501993A CN 202110793571 A CN202110793571 A CN 202110793571A CN 113501993 A CN113501993 A CN 113501993A
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王凤超
董恒星
王陈飞
陈进
张灿云
孔晋芳
李澜
胡蓉蓉
张彦
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Shanghai Institute of Technology
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Abstract

The invention relates to Mn2+The cesium-lead-halogen doped perovskite quantum dot film and the preparation method thereof comprise the following steps: firstly, preparing oleic acid, amino/amino ligand, CsX and PbY2、MnZ2Obtaining a precursor solution; then mixing the precursor solution with toluene to obtain a perovskite quantum dot solution; and finally, placing the film substrate in a perovskite quantum dot solution, performing centrifugal coating, and drying to obtain the perovskite quantum dot film. Compared with the prior art, the method successfully prepares the Mn by adopting the room-temperature one-step centrifugal coating film-making technology2+Doped CsPbX3The method not only enables the film material to maintain the luminescent performance of quantum dots to a great extent, but also has the advantages of simple operation, low cost and the like, and the prepared perovskite quantum dot film material has high crystallization quality and large two-photon emission intensity, so that the material has great application potential in the field of photoelectric devices such as illumination, display and the like.

Description

Mn (manganese)2+Cesium-lead-halogen-doped perovskite quantum dot film and preparation method thereof
Technical Field
The invention belongs to the technical field of photoelectric materials, relates to a perovskite quantum dot thin film material, and particularly relates to Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantum dot thin film and preparation method thereof.
Background
The lead-halogen perovskite material has attractive application potential in the fields of solar cells, lasers, light-emitting devices, biosensors, memories and the like. Particularly in the photovoltaic field, the photoelectric conversion efficiency of the solar cell taking the lead-halogen perovskite as the light absorption layer is dramatically increased from 3.8% to 22.1% in a short seven-year period, and the solar cell has wide market application potential. APbX3(A＝MA+,FA+X ═ Cl, Br, I) type organic-inorganic hybrid perovskite Quantum Dot (QDs) materials have narrow half-peak widths and high-efficiency Photoluminescence (PL) tunable over the entire visible spectral range, but the hydrothermal instability exhibited by the materials limits its further development and application. All-inorganic perovskites (CsPbX) in contrast to organic-inorganic hybrid perovskites3X ═ Cl, Br, I) QDs are excellent candidates for photovoltaic materials, not only having comparable optical properties, but also having higher stability. Although all-inorganic lead-halogen perovskites QDs have many advantages, the high toxicity of lead tends to have serious impact on the environment and public health, thus greatly limiting their practical application in the field of photovoltaics. In order to eliminate the influence of lead toxicity, development and research work of lead-less or lead-free perovskite quantum dot materials are imperative. Ion doping is one of the common approaches to solve the problem of lead toxicity, and transition metal Mn2+It is considered to be a more suitable doping element because of its low toxicity and abundant reserves. In addition, Mn has unique optical properties, so that Mn has unique optical properties2+The doped lead-halogen perovskite quantum dots show two-photon emission characteristics. Mn2+The lead-halogen-doped perovskite quantum dot also has the advantages of adjustable luminescence, long fluorescence life and high photo-thermal stability, and is expected to have new optical, electrical and magnetic properties, so that the material is considered to be a novel perovskite material with wide application prospects in the fields of display, illumination, laser anti-counterfeiting, medical treatment and the like.
At present, Mn doping research in inorganic lead-halogen perovskite quantum dots mostly adopts a high-temperature thermal injection method, but Mn with smaller ionic radius at high temperature2+Ions are easy to migrate to the surface of the quantum dots, so-called self-annealing effect is generated, and Mn is caused2+The doping concentration is low, and then the two-photon emission performance of the material is influenced. Meanwhile, researches show that higher Mn can be realized under the low-temperature condition2+The doping amount is low, but the internal structural defects are high due to the poor crystallization quality of the quantum dot material, so that Mn is generated2+The doped lead-halogen perovskite quantum dot material has poor photoluminescence performance. On the other hand, the preparation of Mn-doped perovskite quantum dot solution and powder material has beenThere are many studies, but the preparation and application studies of the Mn-doped quantum dot thin film material with high luminescence property are relatively few. In addition, in the application process of the quantum dot material, the processing of the quantum dot (such as quantum dot purification, subsequent powder film making and the like) often damages the surface ligand of the quantum dot to cause the dissolution or polymerization reaction of the quantum dot, thereby greatly reducing the luminescence property of the quantum dot. Therefore, in the preparation of Mn with high luminescence property2+On the basis of doping lead halogen perovskite quantum dots, a film preparation method capable of fully maintaining optical performance of the quantum dots is explored to promote Mn2+The application of the doped inorganic perovskite quantum dot material has positive practical significance.
Disclosure of Invention
The invention aims to provide Mn2+A cesium-lead-halogen doped perovskite quantum dot film and a preparation method thereof are used for solving the problem of Mn preparation by the existing high-temperature thermal injection method2+Doped CsPbX3In the process of (X ═ Cl, Br) perovskite quantum dot thin film, Mn is caused by overhigh temperature2+The self-annealing effect is too strong, and the temperature is too low to cause the structural defect of the material, thereby further causing the problem of poor luminous performance of the product.
The purpose of the invention can be realized by the following technical scheme:
mn (manganese)2+The preparation method of the cesium-lead-halogen doped perovskite quantum dot film comprises the following steps:
1) preparing the ligand containing oleic acid, amino group and amino group, CsX and PbY2、MnZ2The precursor solution of (1);
2) mixing the precursor solution with a poor solvent to precipitate cesium, lead and other ions in the poor solvent due to supersaturation, and forming perovskite quantum dots to obtain a perovskite quantum dot solution;
3) placing the thin film substrate in a perovskite quantum dot solution, performing centrifugal film formation, and drying to obtain Mn2+Doping a cesium-lead-halogen perovskite quantum dot film;
wherein the amino/amino ligand comprises one or two of amino ligand or amino ligand, X, Y, Z is at least one of Cl or Br, and the poor solvent isCsX、PbY2、MnZ2A poor solvent of (4).
Further, in step 1), the preparation method of the precursor solution comprises the following steps:
1-1) adding oleic acid and oleylamine into an organic solvent and uniformly mixing;
1-2) adding CsX and PbY2、MnZ2And after being fully dissolved by magnetic stirring, the solution is kept stand for 30-60min to obtain the precursor solution.
Further, in the step 1-1), the amino/amino ligand is oleylamine, and the volume ratio of the oleic acid to the oleylamine is (0.5-1.5): 0.05-0.2;
the organic solvent is N, N-Dimethylformamide (DMF);
the ratio of the total volume of the oleic acid and the oleylamine to the volume of the organic solvent is (0.55-1.7) to 10;
the oleic acid and the oleylamine are used as a dissolution auxiliary reagent of a cesium source lead source, the oleic acid is used for pulling molecular bonds of cesium halide and lead halide apart to generate two intermediate products of cesium oleate and lead oleate, the oleylamine is used for combining with lead to improve the solubility of the lead, and the oleylamine can be used as a passivation ligand to be attached to the surface of the quantum dot after the quantum dot is generated so as to enable the quantum dot to emit light. In terms of concentration, the purity of the oleic acid can be analytically pure (AR) in practical applications, and the concentration of the oleylamine is preferably 80-90%.
In step 1-2), CsX and PbY are used2、MnZ2The molar ratio of (1) - (1-9); the mixed solution has Mn concentration of 0.04-0.31mol/L, and oleic acid and oleylamine as metal ligand and solution stabilizer, and is used for increasing Cs in the step+、Pb2+、Mn2+The solubility of (a).
During the standing process, the solution is in CsPbBr3Achieving high concentrations of Mn in quantum dots2+Doping, increasing the concentration of manganese ions around lead ions in the precursor solution, mixing and reacting the manganese source with the ligand, and allowing Mn to react2+Ion substitution of Pb2+Therefore, the standing time is prolonged to 30-60 min.
Further, in the step 2), the precursor solution is mixed with an aminosilane coupling agent before being mixed with the poor solvent, and the molar ratio of N in the aminosilane coupling agent to Pb in the mixed solution is (0.5-1.2): 1.
Furthermore, the aminosilane coupling agent comprises one or more of 3-Aminopropyltriethoxysilane (APTES), 3-Aminopropyltrimethoxysilane (APTMS) or 3-aminopropylmethyldimethoxysilane.
As a preferable technical scheme, the aminosilane coupling agent is 3-Aminopropyltriethoxysilane (APTES).
Further, in step 2), the poor solvent comprises toluene; the volume ratio of the precursor solution to the toluene is 1 (20-80).
The solvent in the precursor solution is DMF which is Cs+、Pb2+A good solvent for the halide ion compound of (1), make Cs+、Pb2+Greater solubility in DMF, with toluene being Cs+、Pb2+A poor solvent for the halide ion compound of (4). Thus, when the precursor solution was added to toluene, Cs+、Pb2+Precipitate in toluene due to supersaturation and simultaneously form CsPbX3Perovskite quantum dots to obtain CsPbX3Perovskite quantum dot solution.
Further, in step 3), the film substrate includes a flexible substrate such as a PET film.
Further, in the step 3), in the centrifugal film forming process, the centrifugal rotation speed is 2000-4000rpm, and the centrifugal time is 5-10 min.
As a preferable technical scheme, the time from the addition of the aminosilane to the completion of centrifugal film formation is controlled within 10min so as to avoid the premature hydrolysis of the aminosilane to generate a large amount of SiO2Preventing the formation of quantum dots.
In the centrifugal coating process, under a certain rotating speed, the perovskite quantum dots with certain sizes suspended in the solution are separated from the solution by using centrifugal force, so that solid-liquid separation is realized, and in the separation process, the amino ligand, the coupling agent ligand or both play a role in linking the quantum dots coated on the substrate into a film, so that the compactness and the stability of the film are ensured.
Mn (manganese)2+The cesium-lead-halogen doped perovskite quantum dot film is prepared by the method.
The invention adopts a room temperature one-step centrifugal coating film-making technology to successfully prepare Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantum dot thin film materials which largely maintain the luminescent properties of quantum dots; meanwhile, the method has the advantages of simple operation, low cost and the like, and the prepared perovskite quantum dot thin film material has high crystallization quality and large orange-red two-photon emission intensity, so that the material has great application potential in the field of photoelectric devices such as LED luminescence, illumination, display and the like.
Compared with the prior art, the invention has the following characteristics:
1) the invention firstly adds oleic acid and oleylamine as ligands to stabilize Cs+、Pb2+、Mn2+And X-So as to obtain precursor solution with higher concentration, and through stirring, mixing and standing treatment, the manganese source and the ligand are fully mixed and reacted, and the concentration of manganese ions around the lead ions is improved, thereby being beneficial to improving the content of Cs, Pb and Mn in the obtained perovskite quantum dot film, and simultaneously leading Mn to be added2+The ions replace Pb to some extent2+Realizing high Mn/Pb ratio and increasing Mn2+Driving force for diffusion in perovskite quantum dots, thereby in CsPbX3Achieving high concentrations of Mn in quantum dots2+Doping to ensure the optical performance of the quantum dots;
2) the present invention first utilizes an amino group at one end of an amino group ligand and Pb2+Combining, namely replacing amino ligand to attach to the surface of the quantum dot after amino silane is added, thereby passivating Pb dangling bond on the surface of the quantum dot, namely for Pb2+The end capping passivation is carried out, which is beneficial to reducing the non-radiative recombination center on the surface of the quantum dot; meanwhile, in the centrifugal film forming process, after the aminosilane is hydrolyzed, the Si-O bond at the other end can be linked to form amorphous SiO2The quantum dots are surrounded to form a spherical coating layer, so that the influence of the external environment on the quantum dots is isolated, and the light-emitting efficiency of the quantum dots is improvedLight quantum efficiency and stability. Meanwhile, organic groups (amino groups) and inorganic groups (methoxy or ethoxy groups) in the silane can also increase the adhesion with inorganic substrate (such as a glass substrate) and organic substrate (such as the flexible organic substrate) materials, thereby increasing the compactness and stability of the film.
Wherein the hydrolysis process specifically refers to that Si-O bond in aminosilane APTES and APTMS is reacted with methyl (CH) in DMF (strong polar solvent) under the action of-H bond3) Or ethyl (CH)2CH3) Breaking and generating silicon hydroxyl (Si-O-H) intermediate, and the Si-O-H can react with itself or other APTMS or APTES molecules to form Si-O-Si to generate amorphous SiO2And realizing the wrapping of the quantum dots;
3) the invention improves Mn by a normal temperature doping method2+Ion in CsPbX3The concentration of (X ═ Cl, Br) in the perovskite quantum dot lattice can avoid producing strong Mn2+The self-annealing effect can prevent the quantum dots from generating high-concentration structural defects due to too low temperature, thereby being beneficial to ensuring the two-photon emission performance of the quantum dot material;
4) the film is synthesized in the normal temperature atmospheric environment, the quantum dot purification and the film forming are synchronously carried out through low-speed centrifugal coating, and Mn cannot be influenced in the process2+The doping stability in the quantum dot crystal lattice can not cause massive desorption of the ligands on the surface of the quantum dots, so that the quantum dots in the film can largely inherit and maintain the structure and optical performance of the quantum dots in the solution;
5) the invention adopts flexible films such as PET film and the like as the substrate of the perovskite quantum dot film, the flexible substrate can be bent and cut, has strong plasticity and is not easy to crack, and the invention is beneficial to expanding the application of the flexible substrate in the field of photoelectric display;
6) the invention provides a method for preparing Mn2+Doped CsPbX3The method for preparing the (X ═ Cl, Br) perovskite quantum dot film is simple and easy to implement, the cost is low, the obtained quantum dots have strong two-photon emission characteristics, and the method is widely suitable for preparing various ion-doped quantum dot film materials.
Drawings
FIG. 1 shows Mn prepared in example 12+Doped CsPbX3(X ═ Cl, Br) absorption spectra of perovskite quantum dot thin films;
FIG. 2 shows Mn prepared in example 12+Doped CsPbX3(X ═ Cl, Br) band gap diagram of the perovskite quantum dot thin film;
FIG. 3 shows Mn prepared in example 12+Doped CsPbX3X-ray diffraction (XRD) pattern of (X ═ Cl, Br) perovskite quantum dot thin film;
FIG. 4 shows Mn prepared in example 12+Doped CsPbX3PL spectrum of (X ═ Cl, Br) perovskite quantum dot thin film;
FIG. 5 shows Mn prepared in example 12+Doped CsPbX3PL spectrum of (X ═ Cl, Br) perovskite quantum dot solution;
fig. 6 is a comparison of the quantum dot solution in example 1 before (left) and after (right) centrifugation.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Mn (manganese)2+The preparation method of the cesium-lead-halogen-doped perovskite quantum dot film comprises the following steps:
1) uniformly mixing OA, OAm and organic solvent according to the volume ratio of (0.5-1.5): 0.05-0.2): 10; wherein the organic solvent can be N, N-Dimethylformamide (DMF);
2) adding CsX and PbY according to the molar ratio of 1:1 (1-9)2、MnZ2(wherein the Mn concentration is 0.04-0.31mol/L), fully reacting by magnetic stirring, and standing for 30-60min to obtain a precursor solution; wherein X, Y, Z is at least one of Cl or Br respectively;
3) mixing the precursor solution with toluene according to the volume ratio of 1 (20-80) to obtain a perovskite quantum dot solution;
4) placing the cleaned and dried flexible film substrate in a precursor solution, centrifuging for 5-10min at the centrifugal rotation speed of 2000-4000rpm, removing the supernatant and drying to obtain Mn2+Doping a cesium-lead-halogen perovskite quantum dot film;wherein the flexible film substrate can be PET film.
Wherein, in the step 2), after the standing process, the mixed solution can be mixed with a silane coupling agent and used as a precursor solution to carry out the step 3); wherein the silane coupling agent comprises at least one of APTES and APTMS; the molar ratio of N in the silane coupling agent to Pb in the mixed solution is (0.5-1.2): 1.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
mn (manganese)2+Doped CsPbX3The preparation method of the (X ═ Cl, Br) perovskite quantum dot thin film comprises the following steps:
1) 10mL of DMF, 1mL of OA, and 0.2mL of OAm were transferred by a pipette gun, and the resulting mixture was added to a beaker in this order, followed by 0.4mmol of CsBr and 0.4mmol of PbBr2、1.2mmol MnCl2After mixing, fully reacting by magnetic stirring, and standing for 30min to obtain a mixed solution;
2) uniformly mixing 1mL of the mixed solution with 0.04mmol of silane coupling agent APTES to obtain a precursor solution;
3) 100 mu L of precursor solution is dropwise added into 5mL of toluene to obtain Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantum dot solution;
4) cleaning and drying the flexible film substrate, and adding Mn2+Doped CsPbX3And (X ═ Cl, Br) quantum dot solution, then carrying out centrifugal coating for 5min at the centrifugal rotation speed of 3000rpm, removing supernatant, taking out a product, and drying to obtain Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantum dot thin films (as shown in fig. 6). The flexible film substrate can be any one of conventional flexible film substrates such as a PET film substrate, a Low Density Polyethylene (LDPE) film substrate, a chlorinated polyethylene (CSPE) film substrate and the like. The flexible film substrate used in this example was a PET film substrate.
This example also includes the preparation of Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantaAnd (3) carrying out structural performance characterization on the point film, wherein the obtained absorption spectrogram, band gap diagram, XRD (X-ray diffraction) diagram and PL spectrogram are respectively shown in figures 1 to 4.
As can be seen from FIGS. 1 and 2, the band edge exciton absorption of the perovskite quantum dot thin film prepared by the present embodiment occurs in the range of 420-430nm, and the corresponding band gap is about 2.56 eV.
As can be seen from FIG. 3, the crystal structure and tetragonal phase CsPbCl of the perovskite quantum dot thin film prepared in this example3The standard card PDF #18-0366 is very consistent, and has strong diffraction peak and sharp peak shape, which shows that the crystallization quality is better.
As can be seen from FIG. 4, the perovskite quantum dot thin film prepared by the embodiment has the two-photon emission characteristics of 425nm and 600nm, the luminescent color is orange red, the characteristic luminescent peak of manganese at 600nm is very strong, and the high concentration of Mn is confirmed2+And (4) doping effect.
In addition, the present example also provides Mn prepared in step 3)2+Doped CsPbX3The photoluminescence test of the (X ═ Cl, Br) quantum dot solution is shown in fig. 5, and it can be seen from the graph that the PL spectral characteristics of the perovskite quantum dot solution and the perovskite quantum dot thin film are very similar, which indicates that the quantum dots in the thin film fully inherit the optical properties of the quantum dots in the solution.
Example 2:
mn (manganese)2+Doped CsPbX3The preparation method of the (X ═ Cl, Br) perovskite quantum dot thin film comprises the following steps:
1) 10mL of DMF, 1mL of OA, and 0.1mL of OAm were transferred by a pipette gun, and the resulting mixture was added to a beaker in this order, followed by addition of 0.5mmol of CsCl and 0.5mmol of PbBr2、3.5mmol MnCl2After mixing, fully reacting by magnetic stirring, and standing for 30min to obtain a mixed solution;
2) uniformly mixing 1mL of mixed solution with 0.06mmol of silane coupling agent APTMS to obtain precursor solution;
3) 150 mu L of precursor solution is dropwise added into 5mL of toluene to obtain Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantum dot solution;
4) cleaning and drying the PET film substrate, and adding Mn2+Doped CsPbX3And (X ═ Cl, Br) quantum dot solution, then carrying out centrifugal coating for 8min at the centrifugal rotation speed of 3000rpm, removing supernatant, taking out a product, and drying to obtain Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantum dot thin films.
Example 3:
mn (manganese)2+Doped CsPbX3The preparation method of the (X ═ Cl, Br) perovskite quantum dot thin film comprises the following steps:
1) uniformly mixing OA, OAm and DMF in a volume ratio of 0.5:0.2: 10; wherein the volume dosage of OA is 1 mL;
2) CsBr and PbCl are added according to the molar ratio of 1:1:92、MnBr2(wherein the Mn concentration is 0.04mol/L), the mixture is stirred by magnetic force to fully react, then is kept stand for 30min, then is added with silane coupling agent APTMS, and the molar ratio of N in the silane coupling agent to Pb in the mixed solution is 0.5:1, and is mixed uniformly to obtain precursor solution;
3) taking 150 mu L of precursor solution and adding toluene with 20 times of volume to obtain perovskite quantum dot solution;
4) placing the cleaned and dried LDPE flexible film substrate in a precursor solution, centrifuging for 5min at the centrifugal rotation speed of 4000rpm, removing the supernatant and drying to obtain Mn2+Doped CsPbX3(X ═ Cl, Br) perovskite quantum dot thin films.
Example 4:
mn (manganese)2+Doped CsPbCl3The preparation method of the perovskite quantum dot film comprises the following steps:
1) uniformly mixing OA, OAm and DMF in a volume ratio of 1.5:0.05: 10; wherein the volume dosage of OA is 1 mL;
2) CsCl and PbCl are added according to the molar ratio of 1:1:12、MnCl2(wherein the Mn concentration is 0.31mol/L), the mixture is stirred by magnetic force to fully react, then is kept stand for 60min, then is added with silane coupling agent APTES, and the molar ratio of N in the silane coupling agent to Pb in the mixed solution is 1.2:1, and is mixed uniformly to obtain precursor solution;
3) taking 150 mu L of precursor solution and adding toluene with 80 times of volume to obtain perovskite quantum dot solution;
4) placing the cleaned and dried PET flexible film substrate in a precursor solution, centrifuging at 2000rpm for 10min, removing the supernatant, and drying to obtain Mn2+Doped CsPbCl3Perovskite quantum dot thin film.
Example 5:
mn (manganese)2+Doped CsPbBr3The preparation method of the perovskite quantum dot film comprises the following steps:
1) uniformly mixing OA, OAm and DMF in a volume ratio of 1:0.1: 10; wherein the volume dosage of OA is 1 mL;
2) adding CsBr and PbBr according to the molar ratio of 1:1:52、MnBr2(wherein the Mn concentration is 0.2mol/L), the mixture is stirred by magnetic force to fully react, then is kept stand for 40min, then is added with silane coupling agent APTES, and the molar ratio of N in the silane coupling agent to Pb in the mixed solution is 1:1, and is mixed uniformly to obtain precursor solution;
3) taking 150 mu L of precursor solution and adding toluene with 50 times of volume to obtain perovskite quantum dot solution;
4) placing the cleaned and dried PET flexible film substrate in a precursor solution, centrifuging for 8min at the centrifugal rotation speed of 3000rpm, removing the supernatant, and drying to obtain Mn2+Doped CsPbBr3Perovskite quantum dot thin film.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. Mn (manganese)2+The preparation method of the cesium-lead-halogen doped perovskite quantum dot film is characterized in thatThe method comprises the following steps:
1) preparing the ligand containing oleic acid, amino group and amino group, CsX and PbY2、MnZ2The precursor solution of (1);
2) mixing the precursor solution with a poor solvent to obtain a perovskite quantum dot solution;
3) placing the thin film substrate in a perovskite quantum dot solution, performing centrifugal film formation, and drying to obtain Mn2+Doping a cesium-lead-halogen perovskite quantum dot film;
wherein the amino/amino ligand comprises one or two of amino ligand or amino ligand, X, Y, Z is at least one of Cl or Br, and the poor solvent is CsX or PbY2、MnZ2A poor solvent of (4).
2. A Mn according to claim 12+The preparation method of the cesium-lead-halogen-doped perovskite quantum dot film is characterized in that in the step 1), the preparation method of the precursor solution comprises the following steps:
1-1) adding oleic acid and oleylamine into an organic solvent and uniformly mixing;
1-2) adding CsX and PbY2、MnZ2Stirring and standing to obtain the precursor solution.
3. A Mn according to claim 22+The preparation method of the cesium-lead-halogen-doped perovskite quantum dot film is characterized in that in the step 1-1), the amino/amino ligand is oleylamine, and the volume ratio of oleic acid to oleylamine is (0.5-1.5) to (0.05-0.2);
the organic solvent is N, N-dimethylformamide;
the ratio of the total volume of the oleic acid and the oleylamine to the volume of the organic solvent is (0.55-1.7) to 10;
in step 1-2), CsX and PbY are used2、MnZ2The molar ratio of (1) - (1-9); the Mn concentration in the mixed solution is 0.04-0.31 mol/L.
4. A Mn according to claim 12+The preparation method of the cesium-lead-halogen doped perovskite quantum dot film is characterized in that in the step 2), the precursor solution is mixed with an aminosilane coupling agent before being mixed with a poor solvent, and the molar ratio of N in the aminosilane coupling agent to Pb in the mixed solution is (0.5-1.2): 1.
5. A Mn according to claim 42+The preparation method of the cesium-lead-halogen doped perovskite quantum dot film is characterized in that the aminosilane coupling agent comprises one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane or 3-aminopropylmethyldimethoxysilane.
6. A Mn according to claim 12+The preparation method of the cesium-lead-halogen doped perovskite quantum dot film is characterized in that in the step 2), the poor solvent is toluene; the volume ratio of the precursor solution to the toluene is 1 (20-80).
7. A Mn according to claim 12+The preparation method of the cesium-lead-halogen-doped perovskite quantum dot film is characterized in that in the step 3), the film substrate comprises a flexible substrate.
8. A Mn according to claim 72+The preparation method of the cesium-doped lead halide perovskite quantum dot film is characterized in that the flexible substrate comprises a PET film substrate.
9. A Mn according to claim 12+The preparation method of the cesium-lead-halogen doped perovskite quantum dot film is characterized in that in the step 3), in the centrifugal film forming process, the centrifugal rotating speed is 2000-4000rpm, and the centrifugal time is 5-10 min.
10. Mn (manganese)2+The cesium-doped lead-halogen perovskite quantum dot film is characterized by being prepared byPrepared by the process as claimed in any one of claims 1 to 9.
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